JPS60258432A - Method for removing arsenic from copper electrolytic solution or the like by solvent extraction - Google Patents
Method for removing arsenic from copper electrolytic solution or the like by solvent extractionInfo
- Publication number
- JPS60258432A JPS60258432A JP59112803A JP11280384A JPS60258432A JP S60258432 A JPS60258432 A JP S60258432A JP 59112803 A JP59112803 A JP 59112803A JP 11280384 A JP11280384 A JP 11280384A JP S60258432 A JPS60258432 A JP S60258432A
- Authority
- JP
- Japan
- Prior art keywords
- arsenic
- extraction
- organic solvent
- solvent phase
- phase
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052785 arsenic Inorganic materials 0.000 title claims abstract description 67
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title claims abstract description 67
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 26
- 239000010949 copper Substances 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims description 33
- 238000000638 solvent extraction Methods 0.000 title claims description 8
- 239000008151 electrolyte solution Substances 0.000 title claims description 3
- 238000000605 extraction Methods 0.000 claims abstract description 45
- 239000012071 phase Substances 0.000 claims abstract description 45
- 239000008346 aqueous phase Substances 0.000 claims abstract description 18
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 11
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 11
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 8
- 235000011116 calcium hydroxide Nutrition 0.000 claims abstract description 8
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 8
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims description 40
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 33
- 239000003792 electrolyte Substances 0.000 claims description 19
- 229910021529 ammonia Inorganic materials 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 238000005554 pickling Methods 0.000 claims description 5
- 230000001172 regenerating effect Effects 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 abstract description 7
- 239000002904 solvent Substances 0.000 abstract description 6
- 239000013078 crystal Substances 0.000 abstract description 4
- 239000003350 kerosene Substances 0.000 abstract description 2
- 239000003153 chemical reaction reagent Substances 0.000 abstract 2
- GOLCXWYRSKYTSP-UHFFFAOYSA-N Arsenious Acid Chemical compound O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 16
- 230000008929 regeneration Effects 0.000 description 10
- 238000011069 regeneration method Methods 0.000 description 10
- GCPXMJHSNVMWNM-UHFFFAOYSA-N arsenous acid Chemical compound O[As](O)O GCPXMJHSNVMWNM-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000003723 Smelting Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000011575 calcium Substances 0.000 description 4
- 238000011437 continuous method Methods 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 229910052602 gypsum Inorganic materials 0.000 description 4
- 239000010440 gypsum Substances 0.000 description 4
- 238000005201 scrubbing Methods 0.000 description 3
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- DJHGAFSJWGLOIV-UHFFFAOYSA-N Arsenic acid Chemical compound O[As](O)(O)=O DJHGAFSJWGLOIV-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- XPVHUBFHKQQSDA-UHFFFAOYSA-N ammonium arsenate Chemical compound [NH4+].[NH4+].O[As]([O-])([O-])=O XPVHUBFHKQQSDA-UHFFFAOYSA-N 0.000 description 2
- 229940000488 arsenic acid Drugs 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- AIDFJGKWTOULTC-UHFFFAOYSA-N 1-butylsulfonylbutane Chemical compound CCCCS(=O)(=O)CCCC AIDFJGKWTOULTC-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241000473391 Archosargus rhomboidalis Species 0.000 description 1
- RMBBSOLAGVEUSI-UHFFFAOYSA-H Calcium arsenate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-][As]([O-])([O-])=O.[O-][As]([O-])([O-])=O RMBBSOLAGVEUSI-UHFFFAOYSA-H 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 description 1
- AQLMHYSWFMLWBS-UHFFFAOYSA-N arsenite(1-) Chemical compound O[As](O)[O-] AQLMHYSWFMLWBS-UHFFFAOYSA-N 0.000 description 1
- 238000013124 brewing process Methods 0.000 description 1
- 229940103357 calcium arsenate Drugs 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 235000021110 pickles Nutrition 0.000 description 1
- 238000009853 pyrometallurgy Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Extraction Or Liquid Replacement (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は銅電解液等に一４在する砒索分ｔ、該液と有機
溶媒相と全接触させて有機溶媒相中に抽出して除去する
という湿式冶金法に関する。[Detailed Description of the Invention] Industrial Field of Application The present invention is directed to removing the torsion component present in a copper electrolytic solution etc. by bringing the solution into full contact with an organic solvent phase and extracting it into the organic solvent phase. Regarding the hydrometallurgical method.
ここでいう１銅電解液等”とは、銅電解液、および蒸発
濃縮および／又は部分脱調した銅電解液までｔ包含する
浄液工程の砒素含有液、および製錬煙灰または脱銅電解
スライムなどの砒素含有製錬中間物を酸浸出したときに
得られる砒素含有水溶液を意味する。Here, "copper electrolyte, etc." refers to copper electrolyte and arsenic-containing liquid used in the liquid purification process, including copper electrolyte that has been evaporated and concentrated and/or partially deconditioned, and smelting smoke ash or decoppered electrolytic slime. It refers to an arsenic-containing aqueous solution obtained by acid leaching an arsenic-containing smelting intermediate such as.
また、ここでいう１有機溶媒相”とは、例えばりん酸ト
リブチル（ＴＢＰ）、ブチルスルホン戚ジブチルエステ
ル（ＢＰＤＢＥ） 、酸化トリズクチルフオスフイン（
ＴＯＰＯ） 或は４級アンモニウムなどの砒素抽出剤を
含む有機溶媒相を意味する。In addition, "one organic solvent phase" as used herein means, for example, tributyl phosphate (TBP), butyl sulfone related dibutyl ester (BPDBE), trizuctylphosphine oxide (
(TOPO) or an organic solvent phase containing an arsenic extractant such as quaternary ammonium.
非鉄金属製錬、特に銅製錬などで扱う原料鉱石中には若
干の砒素分が存在しておシ、銅製錬工程においての砒素
分の大部分は自溶炉、転炉、精製炉等の乾式製錬工程で
揮発し、煙灰あるいは亜硫酸ガス捕集時のガス洗浄工程
の廃硫酸中に捕集されるが、他の一部は銅電解工程にお
いて銅電解液中に集積されるようになる。し友がって、
銅電解においては砒素分を工程外に除去しない限り系内
に蓄積することが避けられない。A small amount of arsenic is present in the raw material ore used in nonferrous metal smelting, especially copper smelting, and most of the arsenic in the copper smelting process is produced in dry processes such as flash furnaces, converters, and refining furnaces. It volatilizes during the smelting process and is collected in smoke ash or waste sulfuric acid from the gas cleaning process during sulfur dioxide gas collection, but some of it is accumulated in the copper electrolyte during the copper electrolysis process. Be friends,
In copper electrolysis, unless arsenic is removed outside the process, it is inevitable that arsenic will accumulate in the system.
従来技術
上述した事情から、従来、制電′Ｓ液等から砒累分を除
去するための方法が種々提案されている。BACKGROUND OF THE INVENTION In view of the above-mentioned circumstances, various methods have been proposed for removing arsenic buildup from antistatic S liquids and the like.
例えば、銅電解液の浄液工程において脱銅電解という方
法の採用により砒素分を銅とともに電解スライムという
形態で糸外に除去する方法および銅電解液等に硫化水素
ガス？添加して砒素分を除去する方法等があるが、前者
では電解スライムの鋼と砒素の分離が困難であるため、
混合スライムの形態で乾式製錬工程に繰返すので、砒素
分業除去する根本的解決策とはならず、加うるに、脱銅
電解後半ではアルシン（ＡｓＨｌ ）などの有毒ガスの
発生がみられ、その対策としての環境設備に費用を要す
るとともに電流効率も低ドして非能率的となる欠点があ
る。また、後者では硫化水素ガスの反応効率が低いと同
時に銅分の共沈が避Ｖプられず、したがって硫化砒素と
硫化鋼との混合沈澱から銅と砒素と？分離する工程が必
要となる等の欠点があろう
このような状況から、本発明者は、さきに鋼′電解液等
からの砒素分の除去に溶媒抽出法を適用することにニジ
、砒素分を除去する方法を開発した（特公昭５５−１３
５４号〕。この方法は、リン酸トリブチルを含む有機溶
媒相を銅電解液等に接触させると、該準中の砒素分が有
機溶媒相に選択的に抽出し得るという知見に基づくもの
であって、■はとんどエネルギーを消費することなく砒
素分を系外に取り出し得ること、■アルシンのような有
福ガスの発生による作業環境上の問題もないこと、およ
び■砒素分のみ葡遺択的に抽出分離できるため砒素を抽
出した後の有機溶媒相ヵ為ら水相を用いて逆抽出漬液か
ら純粋な亜砒酸を回収し得ること等の従来法にみられな
い利点を有するため、実用的な方法といえるものである
。For example, in the copper electrolyte purification process, a method called decopper electrolysis is used to remove arsenic and copper in the form of electrolytic slime, and hydrogen sulfide gas is used in copper electrolytes. There are methods to remove arsenic by adding it, but in the former method, it is difficult to separate the arsenic from the steel in the electrolytic slime.
Since the pyrometallurgical process is repeated in the form of a mixed slime, it is not a fundamental solution to removing arsenic.In addition, toxic gases such as arsine (AsHl) are generated in the latter half of copper removal electrolysis, and This has the disadvantage that environmental equipment as a countermeasure is costly and the current efficiency is low, resulting in inefficiency. In addition, in the latter case, the reaction efficiency of hydrogen sulfide gas is low and at the same time coprecipitation of copper cannot be avoided. Under these circumstances, the present inventor first decided to apply a solvent extraction method to remove arsenic from steel, electrolyte, etc. developed a method to remove the
No. 54]. This method is based on the knowledge that when an organic solvent phase containing tributyl phosphate is brought into contact with a copper electrolyte, the arsenic content in the quaternary can be selectively extracted into the organic solvent phase. The arsenic content can be taken out of the system without consuming much energy, ■ There is no problem in the working environment due to the generation of arsine-like arifuku gas, and ■ Only the arsenic content can be selectively extracted and separated. This method can be said to be a practical method because it has advantages over conventional methods, such as the ability to recover pure arsenous acid from the reverse extraction solution using an aqueous phase instead of an organic solvent phase after arsenic extraction. It is something.
しかしながら、その後の研究結果がら、この方法にも実
際上程々の問題があることが判明し、それ１）Ｉｓ決す
べく本発明ｔなすに至った。However, subsequent research results revealed that this method also has some practical problems, and in order to solve these problems, the present invention was developed.
発明が解決しようとする問題点
すなわち、上記溶媒抽出による脱砒方法では、砒素全抽
出した後の有機溶媒相の逆抽出に際して少量の水では有
機ｍ媒相の再生が不光分になシ、電解液等からの砒素抽
出効率が低ドする。而して、充分な再生の九めに多量の
水を使用すると工程全体での水バランスの保持が困難と
なり、又、逆抽出漬液からの亜砒酸の回収作業上からも
不利となること等の問題点があることがわかった。The problem to be solved by the invention is that in the above-mentioned method for removing arsenic by solvent extraction, when the organic solvent phase is back-extracted after total arsenic extraction, the organic solvent phase cannot be regenerated with a small amount of water; Arsenic extraction efficiency from liquid etc. is low. Therefore, if a large amount of water is used to achieve sufficient regeneration, it will be difficult to maintain water balance throughout the process, and it will also be disadvantageous in terms of recovery of arsenous acid from the reverse extraction pickle. It turns out that there is a point.
したがって、本＠明は、溶媒抽出によＦ）＠＊電解液か
ら砒素分業除去する方法にみしれる上記問題点を解決し
て、工業的に有利に適用し得る、銅電解液等から溶媒抽
出により砒素分業除去する方法を提供すること２目的と
する。。Therefore, this book solves the above-mentioned problems found in the method of removing arsenic from an electrolyte by solvent extraction, and provides a method for removing arsenic from a copper electrolyte, etc. by solvent extraction, which can be applied industrially advantageously. Two purposes are to provide a method for removing arsenic by extraction. .
以下本発明の詳細な説明する。The present invention will be explained in detail below.
発明の構成
本発明の構成上の特徴は、鯛電解液等全砒素抽出剤業含
む有機溶媒相と接触させて該液中に存在する砒素分葡上
記有機溶媒相に抽出し、ついで該砒索担持有機浴媒相を
水相と接触させて逆抽出することによシ、有機溶媒相か
ら砒素分合水相に離脱させる方法において、上記砒素担
持有機溶媒相’ｔｓ＠酸アンモニウム含有アンモニア水
溶液からなる水相と接触させて逆抽出することによシ、
有機溶媒相から砒素分ｔ−該水相に離脱させることにあ
る。Structure of the Invention The structural feature of the present invention is that the arsenic present in the liquid is extracted into the organic solvent phase by contacting with an organic solvent phase containing a total arsenic extractant such as a sea bream electrolyte, and then the arsenic extract is extracted into the organic solvent phase. In the method of separating the arsenic-containing aqueous phase from the organic solvent phase by bringing the supported organic solvent phase into contact with the aqueous phase and back-extracting the arsenic-containing organic solvent phase, the arsenic-supported organic solvent phase is separated from the arsenic aqueous solution containing ammonium acid. By contacting with the aqueous phase and back-extracting it,
The purpose is to separate the arsenic content from the organic solvent phase into the aqueous phase.
ｔた、本発明は、上記において有機溶媒相から砒素外と
ともに硫酸を水相に離脱させて得られる逆抽出漬液に消
石灰を添加することによル、該逆抽出漬液からアンモニ
アを再生させることもその実施の態様として包含する。In addition, the present invention also provides that ammonia can be regenerated from the back-extracted pickling solution by adding slaked lime to the back-extracted pickling solution obtained by separating sulfuric acid from the organic solvent phase together with arsenic into the aqueous phase. It is included as an embodiment thereof.
本発明に係る溶媒抽出において、砒素抽出剤として例え
ばＴＢＰ 、 ＢＰＤＢＥ 、 ＴＯＰｏ、 ４級アン
モニウムなど全含有する有機溶媒相は、抽出に際しては
そのｔま使用することもできるが、比重および粘度を改
善する目的で：ＩＩＭ当な有機溶剤、例えばケロシンな
どで希釈して使用する場合もあり、さらに数種の抽出剤
を混合して協同効果を期待することもでき、ま九、適当
な改質剤、例えば２−エチルヘキサノールのような高級
アルコールを添加することもできる。銅電解液等と上記
有機溶媒相との接触は、室温（約２０℃）乃至３５℃程
度の温度で行なうとよく、温度が低い力が脱砒率が高く
なる。また、上記接触時の有機溶媒相と銅電解液等（水
溶液相ンとの容を比（以下”０／Ａ比”と称する〕は特
に限定されないがＯ／Ａ比が大きいほど電解液からの脱
砒率が高くなる傾向がある。In the solvent extraction according to the present invention, the organic solvent phase containing all the arsenic extractants such as TBP, BPDBE, TOPo, quaternary ammonium, etc. can be used as is during the extraction, but it is necessary to improve the specific gravity and viscosity. Purpose: IIM may be used diluted with a suitable organic solvent such as kerosene, and several types of extractants may be mixed to expect a synergistic effect; Higher alcohols such as 2-ethylhexanol can also be added. The contact between the copper electrolyte and the organic solvent phase is preferably carried out at a temperature of about room temperature (approximately 20° C.) to 35° C., and the lower the temperature, the higher the arsenic removal rate. The volume ratio between the organic solvent phase and the copper electrolyte (aqueous solution phase) during the above contact (hereinafter referred to as "0/A ratio") is not particularly limited, but the larger the O/A ratio, the more water is removed from the electrolyte. The arsenization rate tends to be high.
上記有機溶媒相による抽出操作は１段の回分力式兼ひに
連続方式もしくは多段の連続方式が可能であるが、砒素
外の抽出を効率よく行なうためＫは向流多段の連続方式
が適している。抽出装置は工業的に一般に用いられてい
るミキサーセトラー抽出装置、回転円板抽出塔、パルス
カラム、遠心抽出機などを使用し得る。The above-mentioned extraction operation using the organic solvent phase can be carried out in a single-stage batchwise and continuous method or in a multi-stage continuous method, but in order to efficiently extract substances other than arsenic, a counter-current multi-stage continuous method is suitable for K. There is. As the extraction device, commonly used industrial mixer-settler extraction devices, rotating disk extraction towers, pulse columns, centrifugal extractors, etc. can be used.
発明の作用効果
本発明は、上述のようにして銅電解液等から有機溶媒相
に抽出した砒素分ｔ、硫酸アンモニウム含有アンモニア
水溶液からなる水相を用いて逆抽出することによって有
機溶媒相から離脱させる方法であって、逆抽出漬液の−
が中性ないしアルカリ性となる１５に操作することＫよ
〕有機溶媒相から砒素分管はぼ完全に除去することが可
能であり、同時に逆抽出後液中の砒素濃度を高めること
も可能である。すなわち、有機ｆＩｊ！Ｘ相中の砒素抽
出剤が完全に再生されるとともに、以下述べるように逆
抽出後液中にアンモニアを再生することも容易とな９、
逆抽出系水相の循積使用が可能となるので、水バランス
の問題点が解消され１同時に逆抽供漬液かうの砒素外の
回収も効率的となる。Effects of the Invention In the present invention, the arsenic extracted from the copper electrolyte etc. into the organic solvent phase as described above is separated from the organic solvent phase by back extraction using an aqueous phase consisting of an ammonia aqueous solution containing ammonium sulfate. A method, comprising:
[K] It is possible to almost completely remove the arsenic fraction from the organic solvent phase, and at the same time, it is also possible to increase the arsenic concentration in the liquid after back extraction. That is, organic fIj! The arsenic extractant in the X phase is completely regenerated, and it is also easy to regenerate ammonia in the liquid after back extraction as described below9.
Since the aqueous phase of the back extraction system can be recycled, the problem of water balance is solved, and at the same time, the recovery of arsenic from the back extraction solution becomes efficient.
本５ＩＪ明の実施にあた都有機溶媒相による銅電解液等
からの砒素外除去に際し、該液中に存在する硫酸も多少
砒素外とともに有機溶媒相中に抽出されるので、この有
機溶媒相から逆抽出により砒素外を離脱するとき硫酸も
同時に離脱される。なお、この逆抽出を行なう前に、最
終的に生成スる石膏の量を低減させる九めに、上記有機
溶媒相を少量の水で洗浄（スクラビングエ＠）シて該溶
媒相中の硫酸の大部分ｔ−線除去ることは極めて有効な
方法であるが、このときにも硫酸の一部が有機溶媒に残
存することは避けられない。When carrying out this 5IJ method, when arsenic is removed from a copper electrolyte using an organic solvent phase, some sulfuric acid present in the solution is also extracted into the organic solvent phase along with the arsenic. When arsenic is removed from the arsenic by back extraction, sulfuric acid is also removed at the same time. Before performing this back extraction, in order to reduce the amount of gypsum that is ultimately produced, the organic solvent phase is washed (scrubbing) with a small amount of water to remove the sulfuric acid in the solvent phase. Although removing most of the t-rays is an extremely effective method, it is inevitable that some sulfuric acid will remain in the organic solvent even in this case.
硫酸アンモニウムを含有するアンモニア水溶液を用いて
逆抽出すると、逆抽出漬液は砒酸アンモニウムと硫酸ア
ンモニウムの混合溶液となるので、本発明に従って、逆
抽出漬液からアンモニアを再生させるために醸成に消石
灰Ｃａ（ＯＨ）ａｔ”添加する。When back-extracted using an ammonia aqueous solution containing ammonium sulfate, the back-extracted pickling solution becomes a mixed solution of ammonium arsenate and ammonium sulfate. According to the present invention, slaked lime Ca(OH)at is added to the brewing process in order to regenerate ammonia from the back-extracted pickling solution. "Added.
アンモニアの再生は下記式（υおよび（２）による。Ammonia regeneration is based on the following formulas (υ and (2)).
Ｌ （ＮＨ４）ＩＡｓ０４＋３Ｃａ （ＯＨ）＊→ｃａ
ｌＡｍｍＯ＋↓＋６ＮＨｓ＋〇ＨｓＯｔｌ）（ＮＨ４）
ｌ ＳＯａ＋Ｃａ Ｃ０Ｈ）＊ ’−＋ Ｃａ ＳＯａ
４１２Ｈ１ρ↓＋２ＮＨｓ （２）しかし、上記のよ
うにしてアンモニアを再生するに当って、９ＯＮ以上の
再生率を得るには１００℃付近までの加熱および／又は
減圧蒸留を行なう必要があるので、そのための設備およ
びエネルギー面でのコスト上昇が避けられない欠点がる
る。L (NH4)IAs04+3Ca (OH)*→ca
lAmmO+↓+6NHs+〇HsOtl) (NH4)
l SOa+Ca C0H)* '-+ Ca SOa
412H1ρ↓+2NHs (2) However, in regenerating ammonia as described above, in order to obtain a regeneration rate of 9ON or more, it is necessary to perform heating to around 100°C and/or distillation under reduced pressure. The disadvantage is that equipment and energy costs inevitably rise.
すなわち、本発明に１９逆抽出に用いられたアンモニア
が過剰の硫酸アンモニウムの存在Ｆで始めて特殊な設備
上必要とせずに逆抽出に要するに充分な量だけ再生され
、しかもそのことにより再生後液が完全に逆抽出液とし
て循環できる途が拓かれ次。That is, in the present invention, the ammonia used in the back extraction is regenerated in sufficient amount for the back extraction without the need for special equipment in the presence of excess ammonium sulfate. This opens the door for it to be recycled as a reverse extraction solution.
以下アンモニア再生工程について具体的実験例を挙げて
説明する。The ammonia regeneration process will be explained below using specific experimental examples.
本実験で用いた合成逆抽出抜液は、Ｉ Ｍ ／ Ｌのア
ンモニアおよび０．５Ｍ／Ｌの硫酸アンモニアを含む水
相上用いて、有機溶媒相（砒素１．７ｇ／４硫酸工、ｓ
ｇ／Ａｔ担持）をＯ／Ａ比＝１０で逆抽出し友ときに得
られたものである。し九がって、７ンモニクム基は２Ｍ
／Ｌ含まれているので、アンモニア再生率５０Ｘのとき
に逆抽出の几めのＩＭ／Ｌのアンモニアが溶液中に再生
されることになる。The synthetic back extraction liquid used in this experiment was used on an aqueous phase containing IM/L ammonia and 0.5 M/L ammonia sulfate, and an organic solvent phase (arsenic 1.7 g/4 sulfuric acid, s
g/At supported) was back-extracted at an O/A ratio of 10. Therefore, the 7-mmonicum group is 2M
/L, so when the ammonia regeneration rate is 50X, IM/L of ammonia will be regenerated into the solution by back extraction.
実験結果は下記に示すとおシである。The experimental results are shown below.
Ｃａ（ＯＨ）＊添力…最 反応温度 アンモニア再生率
１ 倍当量 ２０℃ ２１％
ｉ ｐ ８０〜８５℃ ３０％
１．５１ ６０〜７０℃ ４８％
２ Ｎ ８２〜８６℃ ６９％
３ １ ９０〜９０℃ ７４９１゜
実験結果から明ら力為なように、消石灰添加量１．５倍
当量（０，７５ｍｏｔ／ ｔ ）、反応温度６０〜７０
℃という比較的温和な条件下においてもアンモニア再生
の目的が達成されることになシ、水相は逆抽出に繰夕返
し利用し、沈澱（砒酸カルシウム、石膏および未反応の
消石灰）は次の石膏および亜ヒ酸製造工程で処理するっ
なお、逆抽出系水相の砒酸アンモニウムと消石灰の反応
は、硫酸アンモニウムと消石灰の反応に比較して極めて
優先的で６９、温和な条件（低温。Ca(OH)*Addition... maximum Reaction temperature Ammonia regeneration rate 1 times equivalent 20℃ 21% ip 80-85℃ 30% 1.51 60-70℃ 48% 2 N 82-86℃ 69% 3 1 90~ 90°C 7491° From the experimental results, it is clear that the amount of slaked lime added was 1.5 times equivalent (0.75 mot/t), and the reaction temperature was 60-70°C.
Since the purpose of ammonia regeneration can be achieved even under relatively mild conditions of In the process of producing gypsum and arsenite, the reaction between ammonium arsenate and slaked lime in the aqueous phase of the reverse extraction system is extremely preferential compared to the reaction between ammonium sulfate and slaked lime,69 and under mild conditions (low temperature).
短時間１弱い攪拌等）下では後者の反応は比較的その速
度が遅いため、このアンそニウム再生工程を向流２段の
反応装置で行なうことによって、消石灰使用ｔｔ−更に
少くすることも可能である。Since the latter reaction is relatively slow under short-term (1 weak stirring, etc.) conditions, it is possible to further reduce the use of slaked lime by carrying out this anthonium regeneration process in a two-stage countercurrent reactor. It is.
石膏製造工程では次式により砒酸カルシウムを硫酸で分
解し、石膏を製造し、
ＣａｌＡｍｍ０ａ ＋ ３＆ＳＯ４＋ ２ＨａＯ−２Ｈ
ａＡａ０４＋ ＣａＳＯ４” ２％Ｏ↓（３）ついで、
得られた砒酸浴液を亜硫酸ガスと反応させると、下記式
（４）により砒酸は還元されて亜砒酸になる。In the gypsum production process, calcium arsenate is decomposed with sulfuric acid according to the following formula to produce gypsum, CalAmm0a + 3&SO4+ 2HaO-2H
aAa04+ CaSO4” 2%O↓(3) Then,
When the obtained arsenic acid bath liquid is reacted with sulfurous acid gas, arsenic acid is reduced to arsenous acid according to the following formula (4).
２ＨＩノｋａ０４＋ ２ＳＯ宜ｎ Ａａ宜Ｏａ↓＋２Ｈ
ＩＳＯ４＋ＨｓＯ１４１上記反応に↓り生成しｆｔ Ａ
ｓ１Ｏ１の水に対する溶解度はＡｓ１０１１のそれよシ
小さいので亜砒酸は結晶として効率よく回収することが
できる。2HI no ka04+ 2SO yin Aa yi Oa↓+2H
ISO4 + HsO141 produced by the above reaction ft A
Since the solubility of s1O1 in water is lower than that of As1011, arsenous acid can be efficiently recovered in the form of crystals.
叙上りとおり、本発明によると、銅電解液等からの砒素
分の除去が実質的に効率よく行ない得るとともに、砒素
分を抽出し友後の有機溶媒相からの逆抽出による砒素分
の離脱も効率よく行なりことができ１．加うるに上記離
脱し九砒素分を含む逆抽出後渡からの、逆抽出液として
の硫酸アンモニウム？含有するアンモニア水溶液が簡易
な操作で再生し、これに循環使用することにより逆抽出
系水相を完全クローズド化することができ、かつアンモ
ニア再生に際して生成する沈澱から亜砒酸を有利に回収
し得るという、従来法にみられない実用上の効果が達成
される。As described above, according to the present invention, it is possible to substantially efficiently remove arsenic from a copper electrolyte, etc., and also to remove the arsenic by back extraction from the organic solvent phase after extracting the arsenic. Can be done efficiently 1. In addition, ammonium sulfate as a back-extraction liquid from the back-extraction after-extraction containing nine arsenic components? By regenerating the ammonia aqueous solution contained therein with a simple operation and recycling it, the aqueous phase of the reverse extraction system can be completely closed, and arsenous acid can be advantageously recovered from the precipitate generated during ammonia regeneration. Practical effects not seen in conventional methods are achieved.
以下に最も一般的な砒素抽出剤であるＴＢＰ’ｉ用いた
場合の実施例を示して本発明を更に具体的に説明する。The present invention will be explained in more detail below by showing examples in which TBP'i, which is the most common arsenic extractant, is used.
実施例
Ａｓ４．９１ｇ／ｌおよび＆８０．１９０９／ｌｋ含む
銅電解液？、下記に示す条件で溶媒抽出処理を行なった
。っ
なお、有機溶媒相としてリン酸トリブチル會希１’ｌな
いで用い、マ几、抽出工程、スクラビング工程および逆
抽出工程はいずれもステンレス展の同心円状のきキサー
〇セトラーを用いて向流多段連続方式を適用し７ｔ。Example Copper electrolyte containing 4.91 g/l and &80.1909/lk As? , solvent extraction treatment was performed under the conditions shown below. In addition, 1'l of tributyl phosphate was used as the organic solvent phase, and the matrix, extraction process, scrubbing process, and back-extraction process were all carried out in a multi-stage countercurrent flow using a concentric stainless steel mixer-settler. 7t using continuous method.
抽出工程： ５段 ０／Ａ比＝２ 温度 ３５℃ スクラビング工程： ２段 ０／Ａ比＝１０ 温度 ４５℃ 逆抽出工程＝ ２段 ０／Ａ比冨１０ 温度 ４５℃ 結果は下記に示すとお夕である。Extraction process: 5 stages 0/A ratio=2 Temperature: 35℃ Scrubbing process: 2 stages 0/A ratio=10 Temperature 45℃ Reverse extraction process = 2 stages 0/A Hifu 10 Temperature 45℃ The results are shown below.
上記表にみられるように、原液中の砒素分は実質的に除
去されるとともに、逆抽出により砒素担持有機溶媒相か
らの砒素分の離脱も有効に行なわれる。As shown in the above table, the arsenic content in the stock solution is substantially removed, and the arsenic content is also effectively separated from the arsenic-supporting organic solvent phase by back extraction.
ｔｚ、離脱した砒素分葡含む逆抽出後渡からのアンモニ
アの再生およびこの再生に際して生成した沈澱からの亜
砒酸の回収も１利に行ない得ることがわかる。It can be seen that it is also possible to regenerate ammonia from the back-extraction residue containing the separated arsenic fraction and to recover arsenous acid from the precipitate formed during this regeneration.
なお、本実施例で得られ几石膏中の砒素は０・２６％と
微量であシ、回収された亜砒酸結晶は無色透明な良質の
結晶であった。The arsenic in the phosphogypsum obtained in this example was only 0.26%, which was a very small amount, and the recovered arsenous acid crystals were colorless and transparent crystals of good quality.
出願人 永井忠雄 代理人 宮田広豊Applicant: Tadao Nagai Agent: Hirotoyo Miyata
Claims (1)
させて該液中に存在する砒素分を上記有機溶媒相に抽出
し、ついで該砒素担持有機溶媒相を水相と接触させて逆
抽出することによｐ、有機溶媒相から砒素分を水相に離
脱させる方法において、上記砒素担持有機溶媒相愛硫酸
アンモニウムを含有するアンモニア水浴液からなる水相
と接触させて逆抽出することにより、有機溶媒相から砒
素分′ｆｔ該水相に離脱させることｔ特徴とする銅電解
液等から溶媒抽出により砒素分を除去する方法。 ２ 上ｍｌ逆抽出にＬシ得られた逆抽出漬液に消石灰を
添加することによシ、該逆抽出漬液や為もアンモニアを
再生させる特許請求の範囲第１項記載の方法。 ３、上ｍ逆抽出後液から再生させて得られる、硫酸アン
モニウム含有アンモニア水溶液を上記逆抽出工程へ循環
して利用する特許請求の範囲第２項記載の方法。[Claims] 1. An electrolytic solution or the like is brought into contact with an organic solvent phase containing an arsenic extractant to extract arsenic present in the solution into the organic solvent phase, and then the arsenic-supporting organic solvent phase is In the method of separating arsenic from an organic solvent phase to an aqueous phase by back-extracting the arsenic by contacting with an aqueous phase, the arsenic-supported organic solvent phase is brought into contact with an aqueous phase consisting of an ammonia water bath solution containing ammonium sulfate. A method for removing arsenic from a copper electrolyte or the like by solvent extraction, characterized in that arsenic is removed from an organic solvent phase into an aqueous phase by back extraction. 2. The method according to claim 1, wherein slaked lime is added to the back-extracted pickling solution obtained after the upper ml of back-extraction to regenerate ammonia. 3. The method according to claim 2, wherein an aqueous ammonia solution containing ammonium sulfate obtained by regenerating the liquid after the upper back extraction is recycled to the back extraction step.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59112803A JPS60258432A (en) | 1984-06-01 | 1984-06-01 | Method for removing arsenic from copper electrolytic solution or the like by solvent extraction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59112803A JPS60258432A (en) | 1984-06-01 | 1984-06-01 | Method for removing arsenic from copper electrolytic solution or the like by solvent extraction |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60258432A true JPS60258432A (en) | 1985-12-20 |
| JPS6345457B2 JPS6345457B2 (en) | 1988-09-09 |
Family
ID=14595917
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59112803A Granted JPS60258432A (en) | 1984-06-01 | 1984-06-01 | Method for removing arsenic from copper electrolytic solution or the like by solvent extraction |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60258432A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6455395A (en) * | 1987-08-01 | 1989-03-02 | Henkel Kgaa | Treatment of electrolytic solution of valuable metal |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS551354A (en) * | 1978-06-21 | 1980-01-08 | Toray Ind Inc | Three component conjugate fiber |
-
1984
- 1984-06-01 JP JP59112803A patent/JPS60258432A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS551354A (en) * | 1978-06-21 | 1980-01-08 | Toray Ind Inc | Three component conjugate fiber |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6455395A (en) * | 1987-08-01 | 1989-03-02 | Henkel Kgaa | Treatment of electrolytic solution of valuable metal |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6345457B2 (en) | 1988-09-09 |
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